EP2658651B1 - Compositions à base de nickel pour la préparation de nickel métallique et de complexes de nickel - Google Patents
Compositions à base de nickel pour la préparation de nickel métallique et de complexes de nickel Download PDFInfo
- Publication number
- EP2658651B1 EP2658651B1 EP10838214.4A EP10838214A EP2658651B1 EP 2658651 B1 EP2658651 B1 EP 2658651B1 EP 10838214 A EP10838214 A EP 10838214A EP 2658651 B1 EP2658651 B1 EP 2658651B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- ions
- carbonate
- ligand
- reaction mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 262
- 229910052759 nickel Inorganic materials 0.000 title claims description 128
- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 18
- 150000002815 nickel Chemical class 0.000 title description 45
- 239000003446 ligand Substances 0.000 claims description 105
- 239000007787 solid Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 44
- 239000011541 reaction mixture Substances 0.000 claims description 40
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 39
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 24
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001453 nickel ion Inorganic materials 0.000 claims description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 17
- -1 nickel(II) ions Chemical class 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 41
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 37
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 31
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 25
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 23
- 239000011592 zinc chloride Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 17
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 239000002841 Lewis acid Substances 0.000 description 14
- 150000007517 lewis acids Chemical class 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 12
- 239000012265 solid product Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000005669 hydrocyanation reaction Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical compound CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 description 3
- UWPCLDHZOQJKEQ-UHFFFAOYSA-N 2-(2-hydroxy-3,4-dimethyl-6-propan-2-ylphenyl)-5,6-dimethyl-3-propan-2-ylphenol Chemical compound CC(C)C1=CC(C)=C(C)C(O)=C1C1=C(C(C)C)C=C(C)C(C)=C1O UWPCLDHZOQJKEQ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000005538 phosphinite group Chemical group 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XHOJEECXVUMYMF-IQGLISFBSA-N (2R)-2-[5-[5-chloro-2-(oxan-4-ylamino)pyrimidin-4-yl]-3-oxo-1H-isoindol-2-yl]-N-[(1S)-2-hydroxy-1-(3-methylphenyl)ethyl]propanamide Chemical compound ClC=1C(=NC(=NC=1)NC1CCOCC1)C1=CC=C2CN(C(C2=C1)=O)[C@@H](C(=O)N[C@H](CO)C1=CC(=CC=C1)C)C XHOJEECXVUMYMF-IQGLISFBSA-N 0.000 description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000005323 carbonate salts Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical group C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QDVBKXJMLILLLB-UHFFFAOYSA-N 1,4'-bipiperidine Chemical compound C1CCCCN1C1CCNCC1 QDVBKXJMLILLLB-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 0 C*C1(*)C(*C)(*I)OC(C)*C1(*I)*I Chemical compound C*C1(*)C(*C)(*I)OC(C)*C1(*I)*I 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 150000005840 aryl radicals Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- JRTIUDXYIUKIIE-UHFFFAOYSA-N cycloocta-1,5-diene;nickel Chemical compound [Ni].C1CC=CCCC=C1.C1CC=CCCC=C1 JRTIUDXYIUKIIE-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/322—Hydrocyanation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Definitions
- the invention relates to a method of making a nickel complex with phosphorous-containing ligands. Described are nickel compositions for use in manufacturing nickel metal compositions, and methods of making basic nickel carbonates (BNC) used to produce nickel metal compositions.
- the nickel metal compositions can be used to produce nickel catalyst complexes with phosphorous-containing ligands.
- Hydrocyanation catalyst systems particularly pertaining to the hydrocyanation of ethylenically unsaturated compounds, are known in the art.
- systems useful for the hydrocyanation of 1,3-butadiene (BD) to form pentenenitrile (PN) and in the subsequent hydrocyanation of pentenenitrile to form adiponitrile (ADN) are known in the commercially important nylon synthesis field.
- hydrocyanation of activated ethylenically unsaturated compounds proceeds without the use of a Lewis acid promoter, while hydrocyanation of unactivated ethylenically unsaturated compounds, such as 1-octene and 3-pentenenitrile (3PN), requires the use of a Lewis acid promoter.
- conjugated ethylenically unsaturated compounds e.g., BD and styrene
- strained ethylenically unsaturated compounds e.g., norbornene
- U.S. Patent No. 3,903,120 describes the preparation of zerovalent nickel complexes of the types Ni(MZ 3 ) 4 and Ni(MZ 3 ) 2 A; wherein M is P, As or Sb; Z is R or OR, wherein R is an alkyl or aryl radical having up to 18 carbon atoms and may be the same or different, and at least one Z is OR; A is a monoolefinic compound having 2 to 20 carbon atoms; the R radicals of a given MZ 3 of Ni(MZ 3 ) 2 A preferably being so chosen that the ligand has a cone angle of at least 130°; are prepared by reacting elemental nickel with the monodentate MZ 3 ligand at a temperature in the range of 0°C-150°C in the presence of a halogen-containing derivative of the monodentate MZ 3 ligand as a catalyst. A more rapid reaction is realized by carrying out the preparation in an organonitrile solvent.
- U.S. Patent No. 4,416,825 also describes an improved, continuous process for the preparation of hydrocyanation catalysts comprising zerovalent nickel complexes with monodentate organophosphorus compounds (ligands) by controlling the temperature of the reaction relative to the amount of monodentate ligand and conducting the reaction in the presence of a chlorine ion and organic nitrile such as adiponitrile.
- ligands monodentate organophosphorus compounds
- European Patent No. 0,985,448 describes the preparation of nickel catalysts with a high nickel loading, a high nickel surface area, good sinter resistance and wide pores. This is achieved by including a structural promoter, such as silica, silica-alumina, alumina, zirconia, titania, magnesia or ceria, in the catalyst during the preparation thereof.
- a structural promoter such as silica, silica-alumina, alumina, zirconia, titania, magnesia or ceria
- Ni(COD) 2 nickel bis(1,5-cyclooctadiene)
- a phosphite ligand there are several processes that can be used to make nickel catalyst complexes with phosphorous-containing ligands.
- One method is a reaction between nickel bis(1,5-cyclooctadiene) [NI(COD) 2 ] and a phosphite ligand; however, this process is not very economical because of the high costs of Ni(COD) 2 .
- Another process involves the in situ reduction of anhydrous nickel chloride with zinc dust in the presence of the phosphite ligand. For this reaction to be successful, the nickel metal must react with the phosphorous-containing ligand at a sufficient rate to produce the nickel complex.
- U.S. Patent No. 6,171,996 describes zero-valent nickel complexes comprising bidentate phosphite ligands prepared or generated according to techniques well known in the art, as described, for example, in U.S. Patent Nos. 3,496,217 ; 3,631,191 ; 3,846,461 ; 3,847,959 and 3,903,120 .
- divalent nickel compounds may be combined with a reducing agent, to serve as a source of zero-valent nickel in the reaction.
- Suitable divalent nickel compounds are said to include compounds of the formula NiY 2 where Y is halide, carboxylate, or acetylacetonate.
- Suitable reducing agents are said to include metal borohydrides, metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H 2 .
- bidentate phosphorus-containing ligands In comparison to monodentate phosphorus-containing ligands, bidentate phosphorus-containing ligands generally react more slowly with nickel metals described in the above references.
- nickel metal is the INCO type 123 nickel metal powder ( Chemical Abstract Service registry number 7440-02-0 ), derived from the decomposition of nickel carbonyl at elevated temperatures.
- BNC basic nickel carbonate
- Bidentate ligands may be converted to nickel catalysts that have certain advantages over the nickel catalysts comprising monodentate ligands, especially as olefin hydrocyanation catalysts.
- the INCO type 123 nickel metal powders have insufficient reactivity with the some of these bidentate ligands. Therefore, a nickel metal powder that is sufficiently reactive with bidentate phosphorous ligands and methods of making the nickel metal powder is desirable.
- BNC Basic nickel carbonate
- a basic nickel carbonate which yields a nickel metal that is highly reactive with both monodentate and bidentate phosphorous-containing ligands in forming nickel metal complexes. Also described are methods of making the basic nickel carbonate, since it has also been discovered that precipitation conditions for making the basic nickel carbonate influence the activity of the resulting nickel metal.
- the resulting nickel metal is useful in forming nickel metal complexes for producing pentenenitriles and dinitriles by hydrocyanation.
- the present invention provides a method of making a nickel complex with phosphorous containing ligands, comprising: (i) providing a basic nickel carbonate; and (ii) reducing at least a portion of the basic nickel carbonate of step (i) with a reducing agent to form a nickel-containing solid comprising nickel metal; (iii) reacting the nickel-containing solid with a bidentate phosphorous-containing ligand to form the nickel complex; wherein step (i) comprises: (a) contacting a precipitant solution with a nickel solution in a precipitation reactor to form a reaction mixture; (b) precipitating a basic nickel carbonate from said reaction mixture; wherein said nickel solution comprises nickel(II) ions and water and said precipitant solution is selected from the group consisting of: (i) bicarbonate ions and water, (ii) carbonate ions and water, and (iii) mixtures thereof; and further wherein the mole ratio of bicarbonate ions to nickel ions in the reaction mixture is between 0:1 to
- the precipitant solution is added to the nickel solution, for example, by gradual addition.
- Monodentate A single phosphorous atom that may bond to a single nickel atom to form the nickel complex.
- Bidendate Two phosphorous atoms that may bond to a single nickel atom to form the nickel complex.
- Phosphite An organophosphorous compound comprising a trivalent phosphorous atom bonded to three oxygen atoms.
- Phosphonite An organophosphorous compound comprising a trivalent phosphorous atom bonded to two oxygen atoms and one carbon atoms.
- Phosphinite An organophosphorous compound comprising a trivalent phosphorous atom bonded to one oxygen atoms and two carbon atoms.
- Phosphine An organophosphorous compounding comprising a trivalent phosphorous atom bonded to three carbon atoms.
- the nickel complexes with phosphorous containing ligands can be made by (i) providing a basic nickel carbonate; and (ii) reducing at least a portion of the basic nickel carbonate of step (i) with a reducing agent to form a nickel-containing solid comprising nickel metal; (iii) reacting the nickel-containing solid with a bidentate phosphorous-containing ligand to form the nickel complex; wherein step (i) comprises: (a) contacting a precipitant solution with a nickel solution in a precipitation reactor to form a reaction mixture; (b) precipitating a basic nickel carbonate from said reaction mixture, wherein said nickel solution comprises nickel(II) ions and water and said precipitant solution is selected from the group consisting of: (i) bicarbonate ions and water, (ii) carbonate ions and water, and (iii) mixtures thereof.
- the mole ratio of bicarbonate ions to nickel ions in the reaction mixture at the conclusion of said feeding can range from 0:1 to 2:1, including from 0:1 to 1.6:1, from 0:1 to 1.2:1, from 1.0:0 to 1.9:1, from 1.2:1 to 1.9:1, from 0.8:1 to 1.4:1, from 1.0:1 to 1.8:1, from 1.0:1 to 1.6:1, from 1.0:1 to 1.4:1, from 0.8:1 to 1.4:1, and from 0.8:1 to 1.2:1.
- the mole ratio of carbonate ions to nickel ions in the reaction mixture at the conclusion of said feeding can range from 0:1 to 1.6:1, including from 0:1 to 1.4:1, from 1.0:0 to 1.2:1, from 0.8:1 to 1.4:1, from 1.0:1 to 1.6:1, from 1.0:1 to 1.6:1, from 1.0:1 to 1.4:1, from 0.8:1 to 1.4:1, and from 0.8:1 to 1.2:1.
- Blends of bicarbonates and carbonates can also be used in the precipitant solution.
- the molar ratio has a surprising effect on the resulting nickel metal's effectiveness of reacting with the phosphorous ligands.
- the precipitation reactor may be any suitable containment vessel such as a tank or pipe. Further, the reaction mixture may be agitated prior to and/or during the precipitation of the basic nickel carbonate. For example, agitation may be done by mechanical stirring, pumped circulation loop, flow-through static mixture, or ultrasound.
- the basic nickel carbonate may be precipitated within a temperature range of from 0oC to 90oC, including from 20oC to 90oC, from 20oC to 70oC, from 20oC to 50oC, from 50oC to 90oC, from 60oC to 80oC, and from 65oC to 75oC. Furthermore, the basic nickel carbonate may be precipitated from the reaction mixture in the presence of added carbon dioxide.
- the carbon dioxide can be added to the precipitation reactor, added to the nickel solution, added to the precipitant solution, or added to the reaction mixture, and any combination thereof.
- the precipitant solution may be fed over a period of from 30 minutes to 60 minutes, and can be done in a semi-continuous or continuous manner.
- the precipitant solution can be added to the nickel solution in the precipitation reactor in a semi-continuous or continuous manner, for example, gradual addition.
- the reaction mixture may also be digested after contacting the precipitant solution to the nickel solution by heating the reaction mixture from between 50oC and 90oC for a period of from 0.25 hours to 24 hours.
- Other suitable temperature ranges include from 60oC to 80oC and from 65oC to 75oC.
- Other suitable time periods can range from 2 hours to 24 hours, including from 4 hours to 20 hours, from 6 hours to 16 hours, and from 8 hours to 12 hours.
- the disclosed methods for preparing a nickel complex with phosphorous containing ligands can further comprise, after the precipitation step, washing the precipitated basic nickel carbonate with water; and partially drying the precipitated basic nickel carbonate.
- the precipitated basic nickel carbonate from the reaction mixture is separated from the reaction mixture by filtration or decantation, the resulting precipitated basic nickel carbonate is washed with water by filtration or decantation, and the resulting precipitated basic nickel carbonate is dried by water evaporation between 60oC and 100°C. Drying can be performed under ambient pressure or under vacuum, and in the presence of an inert gas such as nitrogen.
- the nickel solution comprising nickel(II) ions and water, may be prepared by dissolving a nickel(II) salt in water.
- the nickel salt can be any salt that is soluble in water, for example NiCl 2 , NiSO 4 , and Ni(NO 3 ) 2 .
- the precipitant solution, comprising bicarbonate ions may be prepared by dissolving a bicarbonate salt, for example, NaHCO 3 and NH 4 HCO 3 , in water or prepared in-situ by dissolving CO 2 and an alkali metal hydroxide or ammonia in water by known methods.
- the precipitant solution comprising carbonate ions
- the anion of the nickel salt and cation of the bicarbonate or carbonate salt may be selected such that a salt produced from the precipitation, comprising both the cation and anion from the reaction mixture (for example NaCl), is soluble in the water of the reaction mixture.
- a salt produced from the precipitation comprising both the cation and anion from the reaction mixture (for example NaCl)
- Such a selection provides a method for separating said salt product from the precipitated basic nickel carbonate.
- a method of making a nickel-containing solid comprising nickel metal comprises: (i) providing the basic nickel carbonates disclosed above; and (ii) reducing at least a portion of the basic nickel carbonate of step (i) with a reducing agent to form a nickel-containing solid, comprising nickel metal, wherein said nickel-containing solid is adapted to effectively react with a bidendate phosphorous containing ligand to form a nickel complex of the phosphorous-containing ligand.
- the nickel-containing solid is more reactive with phosphorous-containing ligands than nickel-containing solids made by other processes, such as INCO type 123 nickel metal powder, nickel oxide, nickel formate, nickel oxalate, nickel hydroxide, nickel carbonate.
- the high reactivity is partially due to the BNC processes disclosed above, as well as the reducing process.
- the reducing agent can be hydrogen, carbon dioxide, carbon monoxide, methane, ammonia, hydrogen sulfide, merely to name a few nonlimiting examples of suitable reducing agents.
- the amount of bicarbonate or carbonate ions fed relative to the nickel(II) ions charged greatly affects the reactivity of the resulting nickel-containing solid with the phosphorous-containing ligand to make a nickel complex.
- producers of BNC-type nickel compositions would be led to add excess amounts of the precipitant solution so as to recover as much of the nickel as economically feasible.
- the use of excess precipitant produces nickel metal of low reactivity for the phosphorous-ligand complex reaction. Highly reactive nickel is produced when reduced levels of precipitant are used, and presumably more of the nickel(II) ions are allowed to remain dissolved in the water of the resulting reaction mixture.
- the precipitated basic nickel carbonate made using bicarbonate ions filters and washes much faster than the precipitated basic nickel carbonate made using carbonate ions. Also, the filtered precipitated basic nickel carbonate made using bicarbonate ions dries to a soft powder with little shrinkage. For these reasons, producing the nickel-containing solid using bicarbonate ions provides further desirable properties for downstream processing and handling of the dried precipitated basic nickel carbonate.
- the reduction of the basic nickel carbonate with a reducing agent to form a nickel-containing solid may be performed at a temperature in the range from 150oC to 700oC, including from 300oC to 500oC, and from 350oC to 450oC.
- the reduction temperature is from 350 oC to 1500oC, including from 350oC to 450oC.
- the reduction pressure can range from 0.01 atmospheres to 100 atmospheres.
- Reduction may be carried out for a period of at least about 30 minutes using a stoichiometric excess of a reducing agent, such as hydrogen, even though one mole of hydrogen per mole of nickel composition is the theoretical and stiochiometric amount required for reduction.
- the reducing period can be between 1 to 2 hours using a 2:1 mole ratio of hydrogen to nickel composition.
- the nickel containing solids are reacted with a phosphorous-containing ligand to make a nickel complex of the phosphorous-containing ligand.
- Such complexes are useful as a catalyst precursor for at least one of the following reactions:
- the phosphorous-containing ligand may be a monodentate phosphite, stagentate phosphonite, monodentate phosphinite, monodentate phosphine, bidentate phosphite, bidentate phosphonite, bidentate phosphinite, or bidentate phosphine, and any combination of these members. Further, the phosphorous-containing ligand may be a monodentate phosphite to form the nickel complex of the monodentate phosphite then the nickel complex of the monodentate phosphite may be combined with a bidentate phosphorous-containing ligand. Likewise, the phosphorous-containing ligand may be a bidentate phosphite further comprising a monodentate phosphite.
- the bidentate phosphite may be selected from the members of the groups consisting of Formula la, Formula Ib, Formula Ic, or any combination of these members: wherein in Formulae la, Ib, and Ic, R 1 is phenyl, unsubstituted or substituted with one or more C 1 to C 12 alkyl, C 1 to C 12 alkoxy groups, or groups of Formulae A and B, or -(CH 2 ) n OY 2 ; or naphthyl, unsubstituted or substituted with one or more C 1 to C 12 alkyl or C 1 to C 12 alkoxy groups, or groups of Formulae A and B, or -(CH 2 ) n OY 2 ; or 5,6,7,8-tetrahydro-1-naphthyl; wherein in Formulae A and B, Y 1 is independently selected from the group of H, C 1 to C 18 alkyl
- the bidentate phosphite may be selected from the group consisting of Formula VII and VIII, wherein,
- the bidentate phosphite may be selected from the group consisting of Formula IX wherein R 17 is isopropyl, R 18 is hydrogen, and R 19 is methyl; and Formula X wherein R 17 is methyl, R 18 is methyl, and R 19 is hydrogen.
- the reacting of the nickel-containing solid with the monodentate phosphorus-containing ligand may further comprise at least one halogenated catalyst comprising a phosphorus-halide bond selected from the group consisting of PX 3 , R 17 PX 2 , R 18 OPX 2 , [R 19 ][R 21 ]PX, [R 21 ][R 22 O]PX, and [R 23 O][R 24 O]PX; wherein R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are independently selected from the group consisting of C 1 to C 18 hydrocarbyl radicals and each X is a halide independently selected from the group consisting of chloride, bromide, and iodide
- the bidentate phosphorous containing ligands can further comprise at least one Lewis acid promoter.
- the Lewis acid may be selected from the group consisting of inorganic or organometallic compounds in which the cation is selected from the group including scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, europium, ytterbium, tantalum, samarium, and tin.
- the at least one Lewis acid is selected from the group consisting of zinc chloride, ferrous chloride, or a combination of zinc chloride and ferrous chloride.
- the reaction between the nickel-containing solid and the phosphorous-containing ligand may further comprise an organonitrile selected from one or more members of the group consisting of 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenenitrile, 2-methyl-2-bytenenitrile, adiponitrile, 2-metylglutaronitrile, and ethylsuccinotrile.
- organonitrile selected from one or more members of the group consisting of 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenenitrile, 2-methyl-2-bytenenitrile, adiponitrile, 2-metylglutaronitrile, and ethylsuccinotrile.
- Nickel complex or nickel complexes from the reaction of monodentate and bidentate ligands with the nickel-containing solids of this invention may be performed as described in U.S. Provisional Application No. 61/287,757 and the following Examples.
- a 5 wt% solution of a bidentate phosphorus-containing ligand in pentenenitrile solvent further comprising a Lewis acid like ZnCl 2 (0.5 to 2.5 moles Lewis acid per mole bidentate phosphorus-containing ligand) is contacted with the nickel-containing solid of the invention (for example, 4.0 wt% nickel-containing solid).
- Temperatures between 60°C and 80°C give acceptable reaction rates. Sufficient agitation may be used to suspend the nickel-containing solid in this reaction mixture.
- ADN adiponitrile
- BD 1,3-butadiene
- hrs hours
- BNC basic nickel carbonate
- 2M3BN 2-methyl-3-butenenitrile
- MGN 2-methylglutaronitrile
- pentenenitrile or pentenenitriles 4PN, 3PN, 2PN, 2M3BN, and 2M2BN isomers unless specifically limited
- 2PN 2-pentenenitrile including both c2PN and t2PN isomers unless specifically limited
- 3PN 3-pentenenitrile including both c3PN and t3PN unless specifically limited
- 4PN 4-pentenenitrile
- ppm parts per million by weight
- wt% % by weight.
- Ligand A may be prepared by any suitable synthetic means known in the art.
- 3,3'-diisopropyl-5,5',6,6'-tetramethyl-2,2'-biphenol can be prepared by the procedure disclosed in U. S. Published Patent Application No. 2003/0100802 in which 4-methylthymol can undergo oxidative coupling to the substituted biphenol in the presence of a copper chlorohydroxide-TMEDA complex (TMEDA is N,N,N',N'-tetramethylethylenediamine) and air.
- TEDA is N,N,N',N'-tetramethylethylenediamine
- the phosphorochloridite of 2,4-xylenol, [(CH 3 ) 2 C 6 H 3 O] 2 PCl can be prepared, for example, by the procedure disclosed in U.S. Published Patent Application No. 2004/0106815 .
- anhydrous triethylamine and 2,4-xylenol can be added separately and concurrently in a controlled manner to PCl 3 dissolved in an appropriate solvent under temperature-controlled conditions.
- the reaction of this phosphorochloridite with the 3,3'-diisopropyl-5,5',6,6'-tetramethyl-2,2'-biphenol to form the desired Ligand A can be performed, for example, according to the method disclosed in U.S.
- Patent No. 6,069,267 The phosphorochloridite can be reacted with 3,3'-diisopropyl-5,5',6,6'-tetramethyl-2,2'-biphenol in the presence of an organic base to form Ligand A, which can be isolated according to techniques well known in the art, for example as also described in U.S. Patent No. 6,069,267 .
- Ligand A is an example of a compound of Formula I and the Ligand A solutions in 3PN solvent below do not contain any halogenated catalysts of U.S. Patent No. 3,903,120 .
- Example 16 uses a mixture of different monodentate phosphites, Ligand B, that is derived from the reaction of a m-cresol/p-cresol/phenol mixture with PCl 3 .
- a 1 molar NiCl 2 solution (250 mL, 0.25 mole NiCl 2 ) in water is charged to a 1 liter beaker then this solution is magnetically stirred with heating to 70°C. While maintaining this temperature, a precipitant solution comprising bicarbonate ions (25.2 gm of NaHCO 3 dissolved in 400 mL water, 0.30 mole NaHCO 3 ) is fed continuously into the beaker at a rate of 10 mL/min as the reaction mixture is sparged with added CO 2 gas at a rate of 100 mL/min. At the conclusion of the precipitant solution addition, the total moles of bicarbonate ions fed per mole of nickel ions charged is 1.2:1.
- This addition causes a solid product, a BNC composition comprising nickel, to precipitate from the reaction mixture.
- a solid product a BNC composition comprising nickel
- the flow of carbon dioxide gas to the reaction mixture is then terminated and the resulting reaction mixture slurry is then allowed to digest for 2 hours at 70°C.
- this slurry is then filtered using a sintered glass filter, and the solid filter cake is displacement washed with 200 mL water.
- the solid filter cake is then dried in a vacuum oven at 80°C overnight while sweeping nitrogen through the vacuum oven.
- reaction tube Fifteen grams of the dried solid filter cake is then placed inside a reaction tube that can be heated within an electrical furnace located in a lab fume hood. Hydrogen gas flow to the reaction tube is then set at 0.2 liters/minute (about one atmosphere) with any hydrogen off gas from the reaction tube flowing through a bubbler. The temperature of the tube furnace is then increased at a rate of 10°C/minute to a final temperature of 400°C, and then held for one hour at 400°C, after which the reaction tube is allowed to cool under hydrogen flow. After the reaction tube temperature falls below 50°C the flow to the reaction tube is switched to nitrogen gas to purge the hydrogen from the reaction tube.
- Valves on the reaction tube were then closed to prevent exposure of the resulting nickel-containing solid, comprising nickel metal, to air, and the entire reaction tube is transferred to a nitrogen-filled dry lab and the nickel-containing solid emptied into a bottle.
- This nickel-containing solid contains nickel metal as it is attracted to magnets. Exposing these nickel-containing solids to air can reduce rates for the following reaction and/or cause the nickel-containing solids to burn in air to form nickel oxide.
- Nickel complexes are also prepared in this nitrogen-filled dry lab by placing 3.2 gm of this nickel-containing solid, 80 gm of a 5 wt% Ligand A solution in 3PN, and 0.50 gm of anhydrous ZnCl 2 , into a bottle reactor that contained a magnetic stir bar. The nickel-containing solid is not soluble in this reaction mixture. With magnetic stirring, the reaction mixture is then heated rapidly to 80°C, and a filtered sample is withdrawn from this reaction mixture after 30 minutes and is found to contain 1460 ppm nickel, according to a UV-visible or LC analysis, as nickel complexes of Ligand A dissolved in the 3PN.
- a calibrated absorption method that detects the soluble divalent nickel complex (Ligand A)Ni( ⁇ 3 -C 4 H 7 )C ⁇ N-ZnCl 2 by the amount of absorption at a wavelength of 380 nanometers is used.
- This absorption method is calibrated against a LC analysis for total soluble nickel.
- Example 1 The general procedure of Example 1 is repeated in Examples 2 to 5, except that the total moles of bicarbonate ions fed per mole of nickel ions charged is varied from 1.6:1 to 2.0:1 by adjusting the amount of NaHCO 3 dissolved in the 400 mL water to prepare the precipitant solution.
- Results from the reaction of the resulting nickel-containing solids with the Ligand A solution and ZnCl 2 are provided in Table 1.
- Table 1 Effect of the First Molar Ratio, Moles Bicarbonate Ions Fed/Mole Nickel Ions Charged, on the Reaction of the Resulting Nickel-Containing Solid with Ligand A and ZnCl 2 to Produce Nickel Complexes of Ligand A.
- Precipitant Solution Example gm NaHCO3 mole NaHCO3 Moles HCO3 Ions Fed/Mole Ni Ions Charged ppm Ni* 1 25.2 0.30 1.2 1460 2 33.6 0.40 1.6 1390 3 37.8 0.45 1.8 1060 4 39.3 0.47 1.9 823 5 42.0 0.50 2.0 92 *As nickel complexes of Ligand A dissolved in the 3PN.
- Examples 1 through 5 illustrate that as the amount of bicarbonate ions fed is increased relative to the nickel ions charged, there is a decline in the reactivity of the resulting nickel-containing solid with a phosphorus-containing ligand to form soluble nickel complexes. That is, greater amounts of nickel complexes are formed when this first molar ratio, moles bicarbonate ions fed/mole nickel ions charged, is between 0.0:1 and 2.0:1.
- Example 2 is repeated except in the absence of sparging CO 2 gas through the reaction mixture during the feeding of the sodium bicarbonate solution to the 1liter beaker comprising the nickel ions.
- Table 2 greater amounts of nickel complexes are formed from the reaction of the resulting nickel-containing solid with the Ligand A solution and ZnCl 2 when the solid product precipitates in the presence of added CO 2 gas.
- Table 2 Effect of the Presence of Added CO 2 Gas During the Precipitation of the Solid Product on the Reaction of the Resulting Nickel-Containing Solid with Ligand A and ZnCl 2 to Produce Nickel Complexes of Ligand A.
- Precipitant Solution Example gm NaHCO3 mole NaHCO3 Moles HCO3 Ions Fed/Mole Ni Ions Charged ppm Ni* 2 33.6 0.40 1.6 1390 6 33.6 0.40 1.6 965 *As nickel complexes of Ligand A dissolved in the 3PN.
- Example 2 is repeated except that temperatures of the heated NiCl 2 solution, reaction mixture during continuous feeding of the precipitant solution to the 1 liter beaker, and digestion period are 50°C for Example 7 and 90°C for Example 8.
- Example 2 see Table 3
- greater amounts of nickel complexes are formed from the reaction of the resulting nickel-containing solid with the Ligand A solution and ZnCl 2 when the solid product precipitates at 70°C rather than 50°C or 90°C.
- Table 3 Effect of Precipitation Temperature on the Reaction of the Resulting Nickel-Containing Solid with Ligand A and ZnCl 2 to Produce Nickel Complexes of Ligand A.
- Example Heated NiCl 2 Solution Reaction Mixture Digestion Period ppm Ni* 2 70°C 70°C 70°C 1390 7 50°C 50°C 50°C 845 8 90°C 96°C 90°C 850 *As nickel complexes of Ligand A dissolved in the 3PN according to an analysis.
- Example 2 is repeated except substituting NiSO 4 for NiCl 2 . That is, continuously feeding the precipitant solution of Example 2 to a 1molar NiSO 4 solution (250 mL, 0.25 mole NiSO 4 ) in water at 70°C. Similar to solid product precipitated from NiCl 2 , equivalent amounts of nickel complexes are formed (1465 ppm nickel) after 30 minutes from the reaction of the resulting nickel-containing solid with the Ligand A solution and ZnCl 2 when the solid product precipitates from the NiSO 4 solution.
- NiSO 4 for NiCl 2 . That is, continuously feeding the precipitant solution of Example 2 to a 1molar NiSO 4 solution (250 mL, 0.25 mole NiSO 4 ) in water at 70°C. Similar to solid product precipitated from NiCl 2 , equivalent amounts of nickel complexes are formed (1465 ppm nickel) after 30 minutes from the reaction of the resulting nickel-containing solid with the Ligand A solution and ZnCl 2 when the solid product precipitates from the NiSO 4 solution
- a 1 molar NiSO 4 solution (250 mL, 0.25 mole NiSO 4 ) in water is charged to a 1 liter beaker then this solution is magnetically stirred with heating to 70°C. While maintaining this temperature, a precipitant solution comprising carbonate ions (21.2 gm of Na 2 CO 3 dissolved in 400 mL water, 0.20 mole Na 2 CO 3 ) is fed continuously into the beaker at a rate of 10 mL/min but no CO 2 gas is sparged into the reaction mixture. At the conclusion of the precipitant solution addition, the total moles of carbonate ions fed per mole of nickel ions charged is 0.8. This addition also causes a solid product to precipitate from the reaction mixture.
- the resulting reaction mixture slurry is then allowed to digest for 2 hours at 70°C. At the conclusion of this digestion period, this slurry is then filtered using a sintered glass filter, and the solid filter cake is displacement washed with 200 mL water. The solid filter cake is then dried in a vacuum oven at 80°C while sweeping nitrogen through the vacuum oven overnight.
- Example 1 Fifteen grams of the dried solid filter cake is reduced with hydrogen flow at elevated temperatures as described in Example 1. Nickel complexes are also prepared as described in Example 1. A filtered sample is withdrawn from the reaction mixture in the bottle reactor after 30 minutes and is found to contain 1420 ppm nickel, according to a UV-Visible or LC analysis, as nickel complexes of Ligand A dissolved in the 3PN.
- Example 10 The general procedure of Example 10 is repeated in Examples 11 to 13. The difference being that the total moles of carbonate ions fed per mole of nickel ions charged is varied from 1.0:1 to 1.6:1 by adjusting the amount of Na 2 CO 3 dissolved in the 400 mL water to prepare the precipitant solution. Results from the reaction of the resulting nickel-containing solids with the Ligand A solution and ZnCl 2 are provided in Table 4. Table 4. Effect of the Second Molar Ratio, Moles Carbonate Ions Fed/Mole Nickel Ions Charged, on the Reaction of the Resulting Nickel-Containing Solid with Ligand A and ZnCl 2 to Produce Nickel Complexes of Ligand A.
- Precipitant Solution Example gm Na2CO3 mole Na2CO3 Moles CO3 Ions Fed/Mole Ni Ions Charged ppm Ni* 10 21.2 0.20 0.8 1420 11 26.5 0.25 1.0 1340 12 31.8 0.30 1.2 1065 13 42.0 0.40 1.6 0 *As nickel complexes of Ligand A dissolved in the 3PN.
- Examples 10 through 13 illustrate that the reactivity of the resulting nickel-containing solid with a phosphorus-containing ligand to form soluble nickel complexes can decline as the amount of carbonate ions fed is increased relative to the nickel ions charged. That is, greater amounts of nickel complexes are formed when this second molar ratio, moles carbonate ions fed/mole nickel ions charged, is between 0.0 and 1.6.
- Example 5 is repeated except that the order of addition is reversed for the solid precipitation reaction in the 1 liter beaker. That is, the 1 molar NiCl 2 solution is added to the precipitant solution to precipitate a solid product. After digestion, filtration, displacement washing, drying, reducing with hydrogen gas in the reactor tube at 400°C, followed by reacting the resulting nickel-containing solid with the Ligand A solution in 3PN and ZnCl 2 , the filtered sample withdrawn from the reaction mixture is found to contain 0 ppm nickel as nickel complexes of Ligand A dissolved in the 3PN.
- the weight of the dried solid filter cake is also a function of the total moles of bicarbonate (Examples 1 to 9, Table 5) or carbonate ions (Examples 10 to 13, Table 6) fed per mole of nickel ions charged. Table 5. Effect of the First Molar Ratio, Moles Bicarbonate Ions Fed/Mole Nickel Ions Charged, on the Weight of the Dried Solid Filter Cake and Reaction of the Resulting Nickel-Containing Solid with Ligand A and ZnCl 2 to Produce Nickel Complexes of Ligand A.
- Example 1 2 6 7 8 9 3 4 5 14 Precipiating Temperature 70°C 70°C 70°C 50°C 90°C 70°C 70°C 70°C 70°C 70°C Moles HCO3 Ions Fed/Mole Ni Ions Charged 1.2 1.6 1.6 1.6 1.6 1.6 1.8 1.9 2.0 2.0 gm Dried Solid Filter Cake 16.2 21.70 22.1 22.3 15.9 23.5 24.2 26.8 27.6 26.2 ppm Ni* 1460 1390 965 845 850 1465 1060 823 92 0 Table 6.
- nickel-containing solids of Examples 1 to 13 are reacted with the monodentate phosphite Ligand B in 3PN solvent to form nickel complexes, comprising zero-valent nickel and Ligand B, in the absence of a Lewis acid such as ZnCl 2 .
- ZnCl 2 is at least partially separated from the nickel complex of Examples 1 to 12 then the nickel complex of Ligand A contacts BD and HC ⁇ N in a reaction zone.
- a catalyst forms to produce 3PN, 2M3BN, or a combination thereof.
- the same nickel complexes also react with 2M3BN to produce 3PN.
- Nickel complexes of Ligand B of Example 16 contact HC ⁇ N and BD in a reaction zone.
- a catalyst forms to produce 3PN, 2M3BN, or a combination thereof.
- the same nickel complexes also react with 2M3BN to produce 3PN.
- the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC ⁇ N and 3PN in a reaction zone.
- a catalyst forms converting greater than 90% of the 3PN to dinitriles comprising ADN, MGN, and ESN, with an ADN distribution of 95-96%.
- the ADN distribution equals 100% * wt% ADN / (wt% ADN + wt% MGN + wt% ESN), as determined by gas chromatography (GC).
- the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC ⁇ N and 2PN in a reaction zone.
- a catalyst forms converting a portion of the 2PN to 3PN, 4PN, and ADN.
- a Lewis acid promoter like ZnCl 2 , triphenylboron, or compounds of the chemical formula [Ni(C 4 H 7 C ⁇ N) 6 ][(C 6 H 5 ) 3 BC ⁇ NB(C 6 H 5 ) 3 ] 2 as disclosed in U.S. Patent No. 4,749,801
- the nickel complexes of Example 16 contact HC ⁇ N and 3PN in a reaction zone.
- a catalyst forms converting 3PN to dinitriles comprising ADN, MGN, and ESN, wherein ADN is the major dinitrile product.
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Claims (16)
- Procédé de fabrication d'un complexe de nickel avec des ligands contenant du phosphore, comprenant(i) la fourniture d'un carbonate de nickel basique ; et(ii) la réduction d'au moins une partie du carbonate de nickel basique de l'étape (i) avec un agent réducteur pour former un solide contenant du nickel comprenant du nickel métallique ;(iii) la réaction du solide contenant du nickel avec un ligand bidenté contenant du phosphore pour former le complexe de nickel ;dans lequel l'étape (i) comprend :(a). la mise en contact d'une solution de précipitant avec une solution de nickel dans un réacteur de précipitation pour former un mélange de réaction ;(b). la précipitation d'un carbonate de nickel basique à partir dudit mélange de réaction ;dans lequel ladite solution de nickel comprend des ions nickel(II) et de l'eau et ladite solution de précipitation est choisie dans le groupe comprenant : (i) des ions bicarbonate et de l'eau, (ii) des ions carbonate et de l'eau et (iii) leurs mélanges ; et en outre dans lequel le rapport molaire des ions bicarbonate aux ions nickel dans le mélange de réaction est compris entre 0:1 et 2:1 et ledit rapport molaire des ions carbonate aux ions nickel dans le mélange de réaction est compris entre 0:1 et 1,6:1.
- Procédé selon la revendication 1, dans lequel la mise en contact (a) comprend l'ajout de la solution de précipitation à la solution de nickel.
- Procédé selon la revendication 1 ou 2, dans lequel lesdits ions nickel(II) sont choisis dans le groupe constitué de NiCl2, NiSO4 et Ni(NO3)2.
- Procédé selon la revendication 2 ou 3, dans lequel lesdits ions nickel(II) sont NiCl2.
- Procédé selon la revendication 1 ou 2, dans lequel lesdits ions bicarbonate sont choisis dans le groupe constitué de : NaHCO3 et NH4HCO3.
- Procédé selon la revendication 1 ou 2, dans lequel lesdits ions carbonate comprennent Na2CO3.
- Procédé selon la revendication 1 ou 2, comprenant en outre la mise en contact dudit mélange de réaction avec du dioxyde de carbone.
- Procédé selon la revendication 7, dans lequel ladite mise en contact est effectuée en précipitant ledit carbonate de nickel basique.
- Procédé selon l'une des revendications 1 à 8, comprenant en outre la digestion du mélange de réaction avant la précipitation dudit carbonate de nickel basique.
- Procédé selon la revendication 9, dans lequel ladite digestion est effectuée à une température de 50 °C à 90 °C et une durée de 0,25 heure à 24 heures.
- Procédé selon l'une des revendications 1 à 8, dans lequel ladite précipitation dudit carbonate de nickel basique est effectuée à une température de 0 °C à 90 °C.
- Procédé selon la revendication 11, dans lequel ladite température est comprise entre 50 °C et 90 °C.
- Procédé selon la revendication 12, dans lequel ladite température est comprise entre 65 °C et 75 °C.
- Procédé selon l'une des revendications 1 à 8, dans lequel ledit rapport molaire des ions bicarbonate aux ions nickel peut être choisi dans le groupe constitué de : de 0:1 à 1,6:1, de 0:1 à 1,2:1, de 1,0:1 à 1,9:1, de 0,8:1 à 1,4:1, de 1,0:1 à 1,8:1, de 1,0:1 à 1,6:1, de 1,0:1 à 1,4:1, de 0,8:1 à 1,4:1, et de 0,8:1 à 1,2:1.
- Procédé selon l'une des revendications 1 à 8, dans lequel ledit rapport molaire des ions carbonate aux ions nickel peut être choisi dans le groupe constitué de : de 0:1 à 1,4:1, de 1,0:0 à 1,2:1, de 0,8:1 à 1,4:1, de 1,0:1 à 1,6:1, de 1,0:1 à 1,6:1, de 1,0:1 à 1,4:1, de 0,8:1 à 1,4:1, et de 0,8:1 à 1.2:1.
- Procédé selon l'une des revendications 1 à 8, comprenant en outre (c) le lavage dudit carbonate de nickel basique précipité avec de l'eau ; et (d) le séchage partiel du carbonate de nickel basique précipité.
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EP2658651B1 (fr) | 2009-12-18 | 2018-10-17 | INVISTA Textiles (U.K.) Limited | Compositions à base de nickel pour la préparation de nickel métallique et de complexes de nickel |
US9169197B2 (en) | 2010-07-07 | 2015-10-27 | Invista North America S.A. R.L. | Process for making nitriles |
WO2012033556A1 (fr) * | 2010-09-07 | 2012-03-15 | Invista Technologies S.A R.L. | Préparation d'un complexe nickel-ligand phosphoreux |
EP2718015A2 (fr) * | 2011-06-10 | 2014-04-16 | Invista Technologies S.à.r.l. | Perfectionnement à la formation de catalyseur métal-ligand |
JP2014523481A (ja) | 2011-06-10 | 2014-09-11 | インヴィスタ テクノロジーズ エスアエルエル | 流動床反応器を含む焼成プロセス及び還元プロセス |
CN104011014B (zh) | 2011-10-07 | 2016-05-11 | 因温斯特技术公司 | 用于制备腈的方法 |
CN102730771B (zh) * | 2012-05-23 | 2013-11-27 | 吉林市弗兰达科技股份有限公司 | 三步连续法生产高纯无钠高活性复合碳酸镍 |
CN104640872A (zh) | 2012-06-01 | 2015-05-20 | 因温斯特技术公司 | 稳定的配体混合物及用于制备其的方法 |
JP2015523344A (ja) | 2012-06-01 | 2015-08-13 | インヴィスタ テクノロジーズ エスアエルエル | 加水分解触媒およびプロセス |
CN104603146B (zh) * | 2012-09-29 | 2018-01-02 | 诺华股份有限公司 | 环肽类化合物及其作为药物的用途 |
CN104968433B (zh) | 2012-12-07 | 2018-03-09 | 英威达纺织(英国)有限公司 | 改进的戊烯腈制备方法 |
CN109999913A (zh) * | 2012-12-07 | 2019-07-12 | 英威达纺织(英国)有限公司 | 用于改善镍-配体的溶解性的组合物 |
CN103012197B (zh) * | 2012-12-18 | 2015-12-02 | 安徽省安庆市曙光化工股份有限公司 | 3-戊烯腈的制备方法和己二腈的制备方法 |
EP3164238B1 (fr) | 2014-07-02 | 2020-06-03 | INVISTA Textiles (U.K.) Limited | Production de particules métalliques de nickel |
EP3227021A1 (fr) * | 2014-11-20 | 2017-10-11 | Invista North America S.a.r.l. | Nickel ayant une forte activité de complexation de ligand et procédés de fabrication de celui-ci |
CN105502523A (zh) * | 2015-12-17 | 2016-04-20 | 宁波繁盛商业管理有限公司 | 一种碳酸镍的制备方法 |
CN105645482B (zh) * | 2016-02-26 | 2017-08-25 | 金川集团股份有限公司 | 一种氧化亚镍前驱体碳酸镍的合成方法 |
CN108883409A (zh) | 2016-04-22 | 2018-11-23 | 英威达纺织(英国)有限公司 | 非均相催化剂工艺和镍催化剂 |
CN110756820A (zh) * | 2018-07-25 | 2020-02-07 | 荆门市格林美新材料有限公司 | 一种类单球镍粉的制备方法 |
CN108997167B (zh) * | 2018-08-09 | 2021-05-07 | 大连微凯化学有限公司 | 一种利用丁二烯氢氰化制备己二腈和甲基戊二腈的方法 |
CN111218569A (zh) * | 2020-02-28 | 2020-06-02 | 湖南锐异资环科技有限公司 | 一种用于从红土镍矿中提取有价金属的冶炼炉及冶炼方法 |
Family Cites Families (87)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR517898A (fr) | 1916-11-10 | 1921-05-14 | Hermann Berger | Perfectionnements apportés à la préparation des catalyseurs à base de nickel, tels, notamment, que ceux devant etre utilisés pour la transformation des acides gras non saturés et de leurs glycérides en composés saturés correspondants |
CH127157A (de) | 1925-07-22 | 1928-08-01 | Ig Farbenindustrie Ag | Verfahren zur Darstellung eines Nickelkatalysators. |
GB255884A (en) * | 1925-07-22 | 1927-04-28 | Ig Farbenindustrie Ag | Manufacture of nickel catalyst |
NL79307C (fr) | 1951-06-14 | |||
SU116020A1 (ru) | 1958-02-03 | 1958-11-30 | И.М. Вассерман | Способ осаждени основного карбоната никел |
US2913348A (en) | 1958-08-21 | 1959-11-17 | Du Pont | Organic coating composition containing basic nickel carbonate |
US3350167A (en) | 1963-09-26 | 1967-10-31 | Hanson Van Winkle Munning Co | Method of preparing hydrated nickel carbonate and the product thereof |
US3399050A (en) | 1964-04-13 | 1968-08-27 | Sherritt Gordon Mines Ltd | Production of nickel powder |
US3496215A (en) | 1965-11-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins using selected nickel phosphite catalysts |
US3496217A (en) | 1967-05-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins |
CA879003A (en) | 1969-03-28 | 1971-08-24 | The International Nickel Company Of Canada | Separation of nickel from cobalt |
US3655723A (en) | 1969-10-31 | 1972-04-11 | Du Pont | Hydrocyanation of olefins |
US3631191A (en) | 1970-04-08 | 1971-12-28 | Du Pont | Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes |
US3766237A (en) | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
CA975568A (en) | 1972-09-11 | 1975-10-07 | David A. Huggins | Precipitation of nickel carbonate |
SU710958A1 (ru) | 1972-09-15 | 1980-01-25 | Норильский Ордена Ленина И Ордена Трудового Красного Знамени Горно- Металлургический Комбинат Им.А.П.Завенягина | Способ получени основного карбоната никил |
CA970168A (en) | 1972-10-20 | 1975-07-01 | Vladimir N. Mackiw | Production of nickel powder from impure nickel compounds |
US3846461A (en) | 1972-10-25 | 1974-11-05 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
US3847959A (en) | 1972-10-25 | 1974-11-12 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
CA988306A (en) | 1973-04-09 | 1976-05-04 | International Nickel Company Of Canada | Reduction of nickel oxide |
US3903120A (en) | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
CA1038169A (fr) | 1975-06-25 | 1978-09-12 | Inco Limited | Procede de carbonylation |
US4118342A (en) | 1977-06-21 | 1978-10-03 | Labofina S. A. | Process for producing catalysts |
JPS5896802A (ja) | 1981-12-04 | 1983-06-09 | Tadaharu Ogawa | 湿式還元による金属微粉末の製造方法 |
US4416825A (en) * | 1982-02-23 | 1983-11-22 | E. I. Du Pont De Nemours & Co. | Preparation of zerovalent nickel complexes |
NL191511C (nl) | 1983-01-20 | 1995-08-21 | Unilever Nv | Werkwijze voor de bereiding van een nikkel-bevattende katalysator. |
NL190602C (nl) | 1983-12-06 | 1994-05-16 | Unilever Nv | Werkwijze ter bereiding van een nikkel/nikkelsilicaat katalysator en werkwijze voor het hydrogeneren van organische verbindingen daarmee. |
JPS61106422A (ja) | 1984-10-31 | 1986-05-24 | Sumitomo Metal Mining Co Ltd | 高純度塩基性炭酸ニツケルの製造方法 |
US4946068A (en) | 1985-09-30 | 1990-08-07 | Amoco Corporation | Fresh catalyst container |
US4749801A (en) | 1986-06-04 | 1988-06-07 | E. I. Du Pont De Nemours And Company | [Hexakis(pentenenitrilo)nickel II]bis-[μ-(cyano) bis(triphenylborane) (I)], its method of preparation and its use |
JPH0753582B2 (ja) | 1987-12-09 | 1995-06-07 | 株式会社ジャパンエナジー | 炭酸ニッケルの製造方法 |
EP0322049B1 (fr) | 1987-12-21 | 1993-04-07 | Unilever N.V. | Catalyseurs de type nickel sur silice et leur préparation |
NL8901049A (nl) | 1988-08-10 | 1990-03-01 | Unilever Nv | Werkwijze ter bereiding van nikkel/aluminiumoxide-katalysatoren. |
JPH0637308B2 (ja) | 1988-12-26 | 1994-05-18 | 住友金属工業株式会社 | 炭酸ニッケルまたは酸化ニッケルの製造方法 |
JPH03249943A (ja) * | 1990-02-28 | 1991-11-07 | Mitsubishi Heavy Ind Ltd | メタノール改質用触媒 |
JPH075494A (ja) * | 1993-06-18 | 1995-01-10 | Toyo Ink Mfg Co Ltd | エレクトロクロミック層形成用材料およびエレクトロクロミック素子 |
DK0730574T3 (da) | 1993-11-23 | 1999-05-25 | Du Pont | Fremgangsmåder og katalysatorsammensætninger til hydrocyanering af monoolefiner |
DE9405113U1 (de) | 1994-03-25 | 1994-05-26 | Mauser-Werke GmbH, 50321 Brühl | Kunststoff-Behälter |
US5512696A (en) | 1995-07-21 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor |
US5523453A (en) | 1995-03-22 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Process for hydrocyanation |
RU2102137C1 (ru) | 1995-10-09 | 1998-01-20 | Институт нефтехимии и катализа с опытным заводом Академии наук Республики Башкортостан | Способ приготовления никелевого катализатора гидрирования растительных масел и жиров |
US5981722A (en) | 1995-11-20 | 1999-11-09 | Board Of Regents For The University Of Oklahoma | Trypsin inhibitors with insecticidal properties obtained from PENTACLETHRA MACROLOBA |
FR2743010B1 (fr) * | 1995-12-29 | 1998-02-20 | Rhone Poulenc Fibres | Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine |
US5787353A (en) | 1996-03-26 | 1998-07-28 | Southeastern Technologies, Inc. | Process for the in situ recovery of chemical values from UF 6 gaseous diffusion process equipment |
IN191521B (fr) * | 1996-04-02 | 2003-12-06 | Du Pont | |
MY124170A (en) * | 1997-07-29 | 2006-06-30 | Invista Tech Sarl | Hydrocyanation processes and multidentate phosphite ligand and nickel catalyst compositions therefor |
US6069267A (en) | 1997-07-29 | 2000-05-30 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
DE19740180A1 (de) | 1997-09-12 | 1999-03-18 | Basf Ag | Katalysator, umfassend wenigstens einen Nickel(0)Komplex auf Basis eines Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
US7097890B1 (en) | 1998-07-31 | 2006-08-29 | Chevron Phillips Chemical Co. Lp | Polymer with pendent cyclic olefinic functions for oxygen scavenging packaging |
EP0985448A1 (fr) | 1998-08-28 | 2000-03-15 | Engelhard Corporation | Catalyseur à base de nickel |
EP1151814A4 (fr) | 1999-11-12 | 2006-11-02 | Mitsui Mining & Smelting Co | Poudre de nickel et pate conductrice |
JP4385457B2 (ja) | 1999-11-19 | 2009-12-16 | 堺化学工業株式会社 | 微細球状金属ニッケル微粉末の製造方法 |
JP2001335326A (ja) * | 2000-05-24 | 2001-12-04 | Sumitomo Metal Mining Co Ltd | 塩基性炭酸ニッケルの製造方法 |
DE10136488A1 (de) * | 2001-07-27 | 2003-02-06 | Basf Ag | Ni(O) enthaltendes Katalysatorsystem |
TW593251B (en) | 2001-11-26 | 2004-06-21 | Du Pont | Process for preparing 3,3',5,5',6,6'-hexaalkyl-2,2'-biphenols, 3,3',4,4',5,5'-hexaalkyl-2,2'-biphenols and 3,3',4,4',5,5',6,6'-octaalkyl-2,2'-biphenols |
US6660876B2 (en) | 2001-11-26 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions |
US6893996B2 (en) | 2001-11-26 | 2005-05-17 | Invista North America S.A.R.L. | Process for the preparation of a nickel/phosphorous ligand catalyst for olefin hydrocyanation |
FI115522B (fi) | 2001-12-21 | 2005-05-31 | Omg Finland Oy | Metallikarbonaatin valmistusmenetelmä |
FR2842197A1 (fr) * | 2002-07-15 | 2004-01-16 | Rhodia Polyamide Intermediates | Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique |
US20040106815A1 (en) | 2002-12-02 | 2004-06-03 | Ritter Joachim C. | Selective synthesis of organophosphites |
US6906218B2 (en) * | 2002-12-18 | 2005-06-14 | Invista North America S.A.R.L. | Cyclohexane derivatives and methods for their preparation |
FR2849027B1 (fr) | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques |
JP2004323884A (ja) * | 2003-04-23 | 2004-11-18 | Sumitomo Metal Mining Co Ltd | 超微粒子のニッケル粉末及びその製造方法 |
DE102004004682A1 (de) * | 2004-01-29 | 2005-08-18 | Basf Ag | Verfahren zur Herstellung von Adipodinitril durch Hydrocyanierung von 1,3-Butadien |
US7223714B2 (en) | 2004-11-04 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Method of transferring catalyst in a reaction system |
US20060107792A1 (en) | 2004-11-19 | 2006-05-25 | Michael Collins | Method for producing fine, low bulk density, metallic nickel powder |
SE529202C2 (sv) | 2005-05-17 | 2007-05-29 | Sandvik Intellectual Property | Sätt att tillverka en agglomererad pulverblandning av en slurry och agglomererat pulver |
US7854973B2 (en) | 2005-08-09 | 2010-12-21 | Sonoco Development, Inc. | Container and method for making container for oxygen-sensitive products |
CN100363134C (zh) | 2005-11-25 | 2008-01-23 | 北京科技大学 | 一种沉淀-氢还原工艺制备纳米镍粉的方法 |
JP2009530278A (ja) | 2006-03-17 | 2009-08-27 | インビスタ テクノロジーズ エス エイ アール エル | 塩基性添加剤による処理でトリ有機ホスファイトを精製する方法 |
US7544851B2 (en) | 2006-04-25 | 2009-06-09 | Exxonmobil Chemical Patents Inc. | Method of synthesizing aluminophosphate and silicoaluminophosphate molecular sieves |
US7709674B2 (en) | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
US7659422B2 (en) | 2006-07-14 | 2010-02-09 | Invista North America S.A.R.L. | Hydrocyanation process with reduced yield losses |
US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US7709673B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
CN100484882C (zh) | 2006-12-29 | 2009-05-06 | 金川集团有限公司 | 用碳酸钠沉淀生产电子级碳酸镍的方法 |
CA2685668A1 (fr) | 2008-11-24 | 2010-05-24 | Smith International, Inc. | Element de coupe et son procede de fabrication |
CN101478044B (zh) | 2009-01-07 | 2012-05-30 | 厦门钨业股份有限公司 | 锂离子二次电池多元复合正极材料及其制备方法 |
CN101798627B (zh) | 2009-02-09 | 2013-07-03 | 有研稀土新材料股份有限公司 | 一种沉淀稀土的方法 |
CN101519229A (zh) | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | 一种碳酸镍连续合成方法 |
CN101708868B (zh) | 2009-11-20 | 2011-06-15 | 江西核工业兴中科技有限公司 | 碱式碳酸镍或碱式碳酸钴快速生产工艺 |
CN101733106B (zh) * | 2009-12-16 | 2012-08-29 | 南京大学 | 一种担载型镍催化剂的制法 |
EP2658651B1 (fr) | 2009-12-18 | 2018-10-17 | INVISTA Textiles (U.K.) Limited | Compositions à base de nickel pour la préparation de nickel métallique et de complexes de nickel |
WO2011094411A1 (fr) | 2010-01-28 | 2011-08-04 | Packgen | Fût pliable à extrémités renforcées |
WO2012033556A1 (fr) | 2010-09-07 | 2012-03-15 | Invista Technologies S.A R.L. | Préparation d'un complexe nickel-ligand phosphoreux |
EP2718015A2 (fr) | 2011-06-10 | 2014-04-16 | Invista Technologies S.à.r.l. | Perfectionnement à la formation de catalyseur métal-ligand |
JP2014523481A (ja) | 2011-06-10 | 2014-09-11 | インヴィスタ テクノロジーズ エスアエルエル | 流動床反応器を含む焼成プロセス及び還元プロセス |
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2010
- 2010-12-15 EP EP10838214.4A patent/EP2658651B1/fr active Active
- 2010-12-15 WO PCT/US2010/060388 patent/WO2011075496A1/fr active Application Filing
- 2010-12-15 US US12/968,341 patent/US9371343B2/en active Active
- 2010-12-15 JP JP2012544728A patent/JP2013514258A/ja active Pending
- 2010-12-15 WO PCT/US2010/060381 patent/WO2011075494A1/fr active Application Filing
- 2010-12-15 CN CN201080057514.0A patent/CN102655936B/zh active Active
- 2010-12-15 DK DK10838214.4T patent/DK2658651T3/en active
- 2010-12-15 EP EP10838212.8A patent/EP2512673B1/fr active Active
- 2010-12-15 US US12/968,373 patent/US8815186B2/en active Active
- 2010-12-15 KR KR1020127015564A patent/KR20120104252A/ko not_active Application Discontinuation
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Publication number | Publication date |
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EP2512673B1 (fr) | 2016-09-28 |
EP2658651A1 (fr) | 2013-11-06 |
US20110311428A1 (en) | 2011-12-22 |
EP2512673A4 (fr) | 2013-11-20 |
JP2013514258A (ja) | 2013-04-25 |
DK2658651T3 (en) | 2019-01-14 |
CN102655936A (zh) | 2012-09-05 |
US8815186B2 (en) | 2014-08-26 |
US20110196168A1 (en) | 2011-08-11 |
CN102655936B (zh) | 2014-11-05 |
EP2658651A4 (fr) | 2015-11-11 |
KR20120104252A (ko) | 2012-09-20 |
US9371343B2 (en) | 2016-06-21 |
WO2011075494A1 (fr) | 2011-06-23 |
EP2512673A1 (fr) | 2012-10-24 |
WO2011075496A1 (fr) | 2011-06-23 |
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